Graft copolymerization of styrene onto poly(p-nitrophenyl acrylate) by chain transfer reaction

Styrene (St) was polymerized in the presence of poly(p-nitrophenyl acrylate) (PNPA) with azobisisobutyronitrile as an initiator to prepare graft copolymers through the chain transfer reaction of growing polystyrene (PSt) radicals to the aromatic nitro groups on PNPA. The maximum number of branches attained was 16.4 (P _n of PNPA was 1780), which corresponds to 108 monomer units per PSt branch. This is far less than the value of 43, previously obtained for poly(vinyl p-nitrobenzoate) as a trunk polymer. Therefore, several model compounds for trunk polymers were prepared, and the chain transfer constants of PSt radicals to these model compounds were determined. As a result of the Hammett plot, it is concluded that higher electron attracting property of the substituents increases the reactivity of nitro groups to the growing PSt radicals, resulting in more highly branched graft copolymers.     

Grafting onto wool. XX. Graft copolymerization of vinyl monomers by use of redox initiators. Comparison of monomer reactivities

Methyl methacrylate (MMA) and ethylacrylate (EA) have been graft copolymerized onto Himachali wool in aqueous medium by using a ferrous ammonium sulfate–hydrogen peroxide (FAS? H₂O₂) system as redox initiator. Percentage of grafting has been determined as functions of concentration of monomer, molar ratio of [FAS]/[H₂O₂], time and temperature. Percentage of grafting is found to depend upon the molar ratio of [FAS]/[H₂O₂]. An attempt has been made to compare the reactivities of the acceptor monomer (MMA and EA) with that of the donor monomer (VAc) toward grafting onto wool.     

Atom transfer radical polymerization of styrene initiated by 2-(4-chloromethyl-phenyl)-benzoxazole with high activity and fluorescent property

Functionalized polystyrene (PSt) was synthesized utilizing atom transfer radical polymerization (ATRP), which was conducted by using 2-(4-chloromethyl-phenyl)-benzoxazole (CMPB) as initiator, CuCl/PMDETA as catalyst, and cyclohexanone as solvent. The mechanism of ATRP was proved by characterizing the structure of PSt via ¹H NMR and preparing of PSt-b-PMMA block copolymer. The polymerization showed first order with respect to monomer concentration and relatively narrow polydispersity (M_w/M_n range from 1.30 to 1.50). Factors such as different reaction temperatures, mole ratio of monomer to initiator and so on, which can affect the ATRP system, were discussed in the paper. Moreover, CMPB showed high activity and could initiate styrene polymerization even at ambient temperature. The optical property of initiator was well preserved in the obtained PSt, and the end-functionalized PSt exhibited strong fluorescent emission at 351 nm.     

Preparation of gelatin–N-vinylpyrrolidone graft copolymer

The graft copolymerization of N-vinylpyrrolidone (VP) onto gelatin was carried out by the following four different initiator systems: AIBN, K₂S₂O₈, H₂O₂—Fe²⁺, and Ce⁴⁺—HNO₃. The last one caused the monomer to lose the double-bond and polymerization ability due to the hydrolysis of the monomer. Using α,α-azobisisobutyronitrile as an initiator, the graft copolymerization of gelatin and N-vinylpyrrolidone in aqueous medium was studied systematically. The relationships between the rate of grafting and the concentration of initiator, monomer, and gelatin were established experimentally. Meanwhile, the rate equation was also derived from the proposed reaction mechanism, and it was similar to the equation previously obtained experimentally. The apparent activation energies for homopolymerization (E_h), graft copolymerization (E_g), and over all polymerization (E_p) were calculated. The graft efficiency and molecular weight of the grafted PVP were measured by hydrolyzing the backbone with hydrochloric acid. The graft copolymers Gel-g-PVP were added into the coating films, and the physical properties of the films, such as hardening ability, dimensional stability, and wetting property were investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1485–1492, 1998     

Chlorohydrin water swellable rubber compatibilized by an amphiphilic graft copolymer. I. Synthesis and characterization of compatibilizer PVA‐g‐PBA

The graft copolymerization of butyl acrylate onto poly(vinyl alcohol) with ceric ammonium nitrate as redox initiator in a aqueous medium has been investigated. The formation of graft copolymer was confirmed by means of IR, scanning electron microscopy (SEM), and wide‐angle X‐ray diffraction (WAXD). The percentage of mononer conversion and percentage of grafting varied with concentrations of initiator, nitric acid, monomer, macromolecular backbone (X_n = 1750, M = 80 000), reaction temperature and reaction time. Some inorganic salts and organic solvents have a great influence upon grafting. The reaction mechanism has been explored, and rate equations for the reaction are established. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 977–986, 2000     

Graft copolymerization with a new class of acidic peroxo salts as initiator. V. Grafting of methyl methacrylate onto jute fiber using potassium monopersulfate catalyzed by Fe(II)

Graft copolymerization of methyl methacrylate (MMA) onto jute fibers was studied in an aqueous solution using a new class of acidic peroxo salt, potassium monopersulfate, as initiator, under the catalytic influence of Fe(II) under nitrogen atmosphere. The grafting reaction was influenced by the reaction time, temperature, and concentrations of monomer, initiator, and jute fibers. The grafting reactions have also been studied in the presence of various salts and solvents. The maximum grafting percent (385.4%) has been observed at 35°C for the concentration of monomer (1.4082M), initiator (12.9 × 10^?3M), catalyst (2.5 × 10^?4M), and solvent (acetic acid) composition of (40:60) for a reaction time of 6 h. From the experimental results a suitable mechanism for the graft initiation and termination has been put forth. The graft copolymers have been characterized, and their improved properties such as tensil strength tested.     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Grafting vinyl monomers onto polyester fibers. VI. Graft copolymerization of methyl methacrylate onto PET fibers using tetravalent cerium as initiator

The graft copolymerization of methyl methacrylate onto polyester fibers (PET) was investigated using tetravalent cerium as the initiator. The rate of grafting was found to increase progressively with the initiator and monomer concentrations up to 2.5 × 10^?2M and 70.41 × 10^?2M, respectively. The reaction was found to be catalysed by acid up to 15.0 × 10^?2M. The graft yield increased by increasing temperature. The effect of addition of some solvents and thiourea on the rate of grafting was also investigated. A suitable kinetic scheme has been pictured, and rate equations have been derived.     

Trivalent manganese chelate-initiated graft copolymerization of methyl methacrylate onto silk fibers

The graft copolymerization of methyl methacrylate onto silk fibers was investigated in aqueous solution using Mn³⁺ acetyl acetonate [Mn(acac)₃] as initiator. The rate of grafting was determined by varying monomer, acidity of medium, temperature, and reaction medium. The graft yield increases significantly with increase of [Mn(acac)₃] concentration up to 0.01M, and with further increase of [Mn(acac)₃] the graft yield decreases. The effect of the increase of monomer concentration brings about a significant enhancement in the graft yield, and with further increase the graft yield decreases. The rate of reaction is temperature dependent; with increasing temperature, the graft yield increases. Among the solvent composition studied, a water/solvent mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and, with further increase of solvent composition, the graft yield decreases. The effect of some inorganic salts, organic solvents, and complexing agents has been investigated.     

Graft copolymerization of styrene onto poly(vinyl p-nitrobenzoate) by chain transfer reaction

To obtain highly branched graft copolymers, styrene (St) was grafted onto poly(vinyl p-nitrobenzoate) (PVNB) as a trunk polymer through the chain transfer reaction of growing polystyrene (PSt) radicals to the pendent aromatic nitro groups on the trunk polymer. The number of PSt branches increased with St concentration at constant concentrations of PVNB and azobisisobutyronitrile (AIBN) as an initiator, and decreased with AIBN concentration at constant PVNB and St concentrations. The maximum number of branches attained was 43 (P_n of PVNB was 970), which corresponds to 23 monomer units of PVNB per PSt branch. It is confirmed from the results of infrared spectroscopy that the addition of the growing polystyrene radicals occurs not at the benzene rings but at the nitro groups on the benzene rings. Polymerization of St was also carried out in the presence of isopropyl p-nitrobenzoate (IPNB) as a model compound of PVNB. IPNB was found to retard the polymerization of styrene more strongly than PVNB. The chain transfer constant of the polystyrene radicals to IPNB was more than twice as large as that to PVNB.     

Grafting of glycidylmethacrylate onto demineralized xenogeneic bone in aqueous medium

Summary Demineralized xenogeneic bone (DXB) was prepared from bovine cortical tibia and graft copolymerized with glycidylmethacrylate (GMA) using a combination of potassium persulfate (K₂S₂0₈) and sodium metabisulfite (Na₂S₂O₅)as redox initiating system in aqueous medium. To optimize the reaction condition, the concentrations of backbone, monomer, initiator, temperature and time were varied. The percent grafting was found to increase initially and thereafter decrease in most of the cases. The optimum temperature and time were found to be 40°C and 180 minutes, respectively. The grafting results have been discussed and a reaction mechanism is proposed. Functional groups and structural changes of the graft copolymer were determined by Fourier transform infrared (FT-IR) spectroscopic method for proof of grafting and the results are discussed. Received: 12 August 2002/Revised version: 30 October 2002/ Accepted: 25 November 2002 Correspondence to R. Murugan     

Microwave promoted grafting of acrylonitrile onto Cassia siamea seed gum

Cassia siamea seed polysaccharide was grafted with acrylonitrile under microwave (MW) irradiation without adding any radical initiator or catalyst. Free radicals are generated here due to the dielectric heating caused by the localized rotation of the hydroxyl groups at the polysaccharide backbone and initiate grafting. To obtain the optimal conditions for the microwave promoted grafting, effect of reaction variables such as monomer/seed gum concentration; MW power and exposure time on the graft copolymerization was studied and the maximum %grafting (%G) and %efficiency (%E) observed were 150% and 43.54%, respectively. The representative graft copolymer was characterized by Fourier transform‐infrared, Thermogravimetric analysis and X‐ray diffraction measurement, taking C. siamea gum as reference. At the same monomer concentration, K₂S₂O₈/ascorbic acid initiated grafting onto the seed gum could result into 80% grafting with 23.22% efficiency. Various properties of the MW synthesized grafted gum like water/saline retention, water retention after saponification and viscosity of the gum solutions were studied. The results have been compared with the conventionally synthesized grafted gum and the parent gum. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2384–2390, 2006     

Grafting vinyl monomers onto silk fibers. X. Graft copolymerization of methyl methacrylate onto silk using hydrogen peroxide–thiourea redox system

The graft copolymerization of methyl methacrylate onto silk fibers initiated by a hydrogen peroxide–thiourea redox system was investigated under various conditions. The effects of monomer, initiator, temperature, acidity of the medium, and solvent on the rate of grafting were studied. The graft yield increases with the increase of monomer and initiator concentration. The graft yield also increases with the increase of acid concentration upto 22.50 × 10^?2M and thereafter it decreases. The effect of some inorganic salts on the rate of grafting has also been investigated, and a suitable mechanism has been suggested.     

Grafting vinyl monomers onto silk fibers. VIII. Graft copolymerization of methyl methacrylate onto silk using tetravalent manganese–oxalic acid redox system

The graft copolymerization of methyl methacrylate onto silk fibers was investigated in aqueous solution using the Mn(IV)–oxalic acid redox system. The copolymerization reaction was carried out under a variety of conditions such as different monomer, initiator, oxalic acid, acid concentrations, and temperatures. The graft yield increases with increasing initiator concentration up to 5 × 10^?2M, and with further increase of the initiator concentration it decreases. The graft yield also increases with increasing sulfuric acid concentration up to 15 × 10^?2M, and decreases thereafter. The rate of grafting also increases with increase in oxalic acid concentration up to 1.5 × 10^?2M and 84.592 × 10^?2M, respectively, and thereafter the rate of grafting shows down. The effect of temperature, solvents, and salts on graft yield has also been investigated and a plausible rate expression has been derived.     

Chemical modification of jute fibers. II: A study on the Fe2+/H2O2-initiated graft copolymerization of methyl methacrylate,acrylonitrile, and acrylamide onto jute fibers

The study of graft copolymerization of methyl methacrylate, acrylonitrile, and acrylamide onto both defatted and bleached jute fibers using the ferrous ammonium sulfate / H₂O₂ redox initiator system has been made. To determine the optimum conditions of grafting, the effects of concentrations of ferrous ammonium sulfate, monomer, H₂O₂; time and temperature on percentage of graft yield have been studied. Acrylamide was found to graft onto the fiber only at a fixed ferrous ammonium ion concentration (5 × 10^?4M). Kinetic studies showed that the rates of grafting follow the second-order mechanism. The activation energies of the reactions were found to be 3.351 and 2.53 kcal/mol in the methyl methacrylate and acrylonitrile systems, respectively. The grafted fibers have been characterized by thermogravimetric analysis, IR spectroscopy, and XRD studies.     

Graft copolymerization of vinyl monomers onto modified cottons. XII. Grafting of 1,1-dihydroperfluoroheptyl acrylate onto cellulose carbamate using hydrogen peroxide as initiator

Cellulose carbamate having 1.4% N was grafted with 1,1-dihydroperfluoroheptyl acrylate (DHPFHA) using H₂O₂ as initiator under a variety of conditions. The technique used involved padding the fabric in H₂O₂ solution at room temperature followed by impregnating it in an aqueous emulsion of DHPFHA. The graft yield, expressed as fluorine percent, was found to depend upon monomer and initiator concentration, temperature, and reaction time and pH of the polymerization medium as well as upon the carbamate content of the modified cotton. Increasing the monomer concentration up to 5% caused a considerable enhancement in grafting. The same holds true for initiator concentration up to a certain limit after which the grafting decreases. Raising the reaction temperature up to 100°C was accompanied by an increment in the magnitude of grafting reaction. The latter was characterized by an initial fast rate followed by a slower rate. Slightly acidic media (pH 5–6) proved to be the best for performing grafting. The graft yields were quite poor when grafting was carried out in acidic (pH 2–4) or alkaline (pH 8–12) media. The presence of a relatively smaller amount of carbamate groups in the cellulose molecules decreases its susceptibility to grafting. The opposite holds true for larger amounts. Incorporation of FeSO₄ at low concentration in the monomer emulsion had no effect on the graft yield. However, the latter decreases at higher FeSO₄ concentration. Grafted cellulose carbamate having ca. 15% fluorine showed very good oil and water repellency. The grafted product retained ca. 85% of the strength of cellulose carbamate.     

Kinetics and mechanism of free radical grafting of methyl acrylate onto sago starch

The graft copolymerization was carried out by methyl acrylate with sago starch in which ceric ammonium nitrate was used as an initiator. It has been found that the rates of graft polymerization and grafting efficiency were dependent upon the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU, anhydro glucose unit), mineral acid (H₂SO₄), and as well as reaction temperature and period. A rate equation of polymerization was established from the proposed reaction mechanism, and the rate of polymerization (R_p) was the first‐order dependence of the MA monomer concentration and square root of the CAN concentration. A new kinetic model of the grafting reaction has been proposed, and a normal kinetics of methyl acrylate polymerization was observed. An equation of a predicted model relating the graft fraction of poly(methyl acrylate) with the sago starch has been derived, and validity of the predicted model was verified by the experimental results. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 784–791, 2000     

Synthesis of poly(cyclohexene oxide)‐block‐polystyrene by combination of radical‐promoted cationic polymerization,atom transfer radical polymerization and click chemistry

The combination of radical‐promoted cationic polymerization, atom transfer radical polymerization (ATRP) and click chemistry was employed for the efficient preparation of poly(cyclohexene oxide)‐block‐polystyrene (PCHO‐b‐PSt). Alkyne end‐functionalized poly(cyclohexene oxide) (PCHO‐alkyne) was prepared by radical‐promoted cationic polymerization of cyclohexene oxide monomer in the presence of 1,2‐diphenyl‐2‐(2‐propynyloxy)‐1‐ethanone (B‐alkyne) and an onium salt, namely 1‐ethoxy‐2‐methylpyridinium hexafluorophosphate, as the initiating system. The B‐alkyne compound was synthesized using benzoin photoinitiator and propargyl bromide. Well‐defined bromine‐terminated polystyrene (PSt‐Br) was prepared by ATRP using 2‐oxo‐1,2‐diphenylethyl‐2‐bromopropanoate as initiator. Subsequently, the bromine chain end of PSt‐Br was converted to an azide group to obtain PSt‐N₃ by a simple nucleophilic substitution reaction. Then the coupling reaction between the azide end group in PSt‐N₃ and PCHO‐alkyne was performed with Cu(I) catalysis in order to obtain the PCHO‐b‐PSt block copolymer. The structures of all polymers were determined. Copyright © 2010 Society of Chemical Industry     

Grafting of polymeric side chains to gelatin

Kinetics of grafting of poly(butyl acrylate) onto gelatin was studied with H₂O₂—ascorbic acid redox systm. Percent grafting, grafting efficiency, R_g, and R_h were determined as a function of time, temperature, initiator, monomer, and backbone concentration. It was found that R_g depends on first power of monomer concentration and 0.5 power to the initiator concentrations. A detailed kinetic scheme is proposed to explain these results.     

Grafting of acrylonitrile onto styrene-maleic acid copolymer by tetravalent cerium ion

The graft copolymerization of acrylonitrile (AN) onto a styrene-maleic acid copolymer (SY-MAc) with ceric ammonium nitrate (CAN) as a redox initiator in an aqueous medium has been studied. The effects of various reaction parameters, including reaction time and temperature, concentrations of initiator, nitric acid, and monomer, on the grafting yields and the rates of polymerization (R_p), graft copolymerization (R_g), and homopolymerization (R_h) were studied systematically. The results are discussed. The kinetic scheme of free-radical graft copolymerization has been proposed and the equations relating the values of R_p, R_g, and R_h are also suggested. The experimental results are found to be in good agreement with the proposed kinetic scheme. The activation energies of graft copolymerization and total polymerization are calculated. © 1995 John Wiley & Sons, Inc.